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By P. R. Gage, R. W. Bartlett

At high temperatues and reduced oxygen pressuves, molybdenum silicicles oxidize to form SiO(g) vathev than a passivating SiO2 film. This is a sevious problem for low-pressure applications of sili-cide-coated rejvactory tnetals. As oxiclalion pvoceeds, the higher oxidntion potential of silicon initially suppresses oxidation of molybdenum and silicon is depleted near the surface. Eventually, silicon depletion causes secondary passivation (SiO2) mid an active to passiue transition in oxidntion behavior at moderately low pressures. At very low pressures, silicon depletion continues until steady-state oxidation of both silicon and rnolyhdenum can proceed at rates propovtional to their initial stoicliiorrzetvies. Ohsel-vations of 'oxidatiou-rate belzcriliov at temperatures from 1101° to 1700°C and oxygen pressures from 10-7 to 1 at in were made using thermogravimetn'c, X-ray diffraction, and elect?*on-rtric?ro/,vobe techniqrres. The experimental results are in good agreement with calculated lirnits for the various types of behavior that were based on tlievtnochernicnl atzd dffusion rate data for the Mo-Si system. A protective oxide film normally forms during the oxidation of elemental silicon. However, at elevated temperatures and reduced pressures this film is not present and oxidation is rapid. wagnerl has shown that this behavior occurs because SiO(g) is more stable than SiO2. The behavior of the silicides at high temperatures is similar but more complicated. Molybdenum and several silicide compounds are involved and the chemical activity of silicon, or the equivalent silicon vapor pressure, can vary considerably in these phases. Also, diffusion in the silicides resulting from reactions in which a higher silicide is reduced to a lower silicide, or molybdenum containing dissolved silicon, must be considered. EXPERIMENTAL AND ANALYTICAL METHODS Isothermal oxidation experiments were conducted using hot-pressed MoSi2 and Mo5Si3 wafers. Each experiment was conducted at a fixed oxygen pressure by controlling the flow of oxygen in and out of the furnace chamber. Most of the experiments were conducted in a molybdenum-wound tube furnace. Special construction features, including use of a high-purity dense A12O3 refractory tube, permitted operation in high vacuum to 1500°C. Higher temperatures could be obtained at higher working pressures and with a sacrifice of tube lifetime. Temperature was measured with three Pt 6 pct Rh/Pt 30 pct Rh thermocouples and controlled with a proportional controller. Weight changes were monitored with a quartz spring balance. The few experiments, at higher temperatures and low pressures, were conducted in a cold wall vacuum chamber using induction heating with direct susceptance of the sample. Because of the variable levitation effect of the induction coil on the sample, weight changes could not be monitored continuously in these experiments. All samples representing both experimental methods were weighed before and after oxidiation and examined with a microscope and analyzed by X-ray diffraction. The analytical treatment assumes equilibrium at interfaces and uses existing thermodynamic data. For convenience, equilibria are expressed as chemical potentials or as vapor pressures of the gases involved. The resulting differences in equilibrium vapor pressure between adjacent interfaces and between the surface and external atmosphere drive diffusion processes in the solid and gas boundary film, respectively. These diffusion processes govern the rate of oxidation. A bibliography of the sources of thermochemical data for the reactions pertinent to the Mo-Si-O system is given in Table I. Reactions are listed with the sources of free-energy data referenced. Since all of these reactions involve one or more gas species, usually oxygen, a plot of the product-gas chemical potential, -RT In Pg, vs absolute temperature for each reaction is given in Fig. 1. These curves can be used to determine equilibrium vapor pressures or to compare the stability of different compounds in the various gases: O2, Si, SiO, and Moo3,. The data of Table I and Fig. 1 were used to determine the analytical results presented in this paper. EXPERIMENTAL RESULTS The weight changes for three MoSi, samples oxidized at 1500°C are plotted against time in Fig. 2. The treatments were identical except for the indicated variance of oxygen pressure and each curve represents one of three characteristic types of behavior that were observed. The upper curve is an example of passive oxidation, which is defined as

Jan 1, 1965

By R. R. Joseph, K. A. Gschneidner

The solid solubility of magnesium in the close-packed modifications of lanthanum, cerium, praseodymium, neodymium, gadolinium, dysprosium, and lutetium was determined from approximately 250°C to the eutectoid temperature by the X-ray parametric technique. The maximum solubility at the eutectoid temperature was found to be 9.4 at. pet in La, 8.2 in Ce, 9.2 in Pr, 8.2 in Nd, 14.1 in Gd, 13.5 in Dy, and 11.5 in Lu. The solubility when compared at a homologous temperature was found to increase in a smooth manner with decreasing size factor from lanthanum to lutetium. It was found that the apparent atomic radius of magnesium when dissolved in the lanthanide solvent was constant and could be accounted for by consideration of several models dealing with departures from Vegard's law. The eutectoid temperatures for the lanthanide-rich La-Mg, Ce-Mg, and Nd-Mg systems were found to be 544", 505°, and 551°c, respectively. A study of the solid solubility of magnesium in the lanthanide metals was initiated because the valency and electron egativity difference are essentially constant and favorable for solid-solution formation, and thus one could examine the effect of size on terminal solid solutions. The size factors based on metal radii range from 14.6 pet for lanthanum to 7.5 pet for lutetium. Since the electronegativity difference is small, 0.06 unit or less, application of the Hume-~othery' and Darken and Gurry2 criteria for solid-solution formation indicates that the solubility of magnesium would be expected to be small for lanthanum (between 5 and 10 at. pet) and to increase as we proceed along the lanthanide series. A search of the literature revealed no data on the solubility of magnesium in the lanthanide metals except for the solubility of magnesium in cerium at 450oCA typical phase diagram for the lanthanide-rich end of the lanthanide-magnesium phase diagram is shown in Fig. 1. EXPERIMENTAL PROCEDURES Preparation of Alloys. The lanthanide metals used in the preparation of alloys for this investigation were prepared from the corresponding fluoride by metallothermic reduction techniques previously described by Daane.4 The chemical analyses of the metals used are listed in Table I.

Jan 1, 1965

By R. E. Tate, L. J. Herman

We have had occasion to produce wire of Np-237 in small diameters for use in some chemical experiments. Since the mechanical metallurgy of neptunium has not been investigated extensively, it seems desirable to report our successful extrusion technique. Because of the neptunium activity and its attendant health hazard the experimental work was done in glove boxes and related equipment also used for Pu-239. At room temperature a phase neptunium' is a hard (Dph -355) orthorhombic metal of high density (p = 20.45 g per cu cm). a neptunium transforms2 to tetragonal ß neptunium at about 280°C and this in turn transforms to bcc y neptunium at about 577°C. The y phase melts at about 637°C. A temperature of 340° to 345°C was selected for the extrusion, this temperature being a compromise be- tween a possible advantage of working with the presumably more plastic cubic y phase above 577°C and the risk of having the neptunium react with the alloy steel die to form the low-melting Fe-Np eutectic. A 0.75-in.-long, 0.26-in.-diameter ingot of good-purity* Np-237 was extruded by the direct *C = 230 ppm, Pu = 200 ppm, thirty-five metallic elements below limit of detection by spectrographic methods. process through flat-face orifices to form several sizes of wire ranging from 0.010 to 0.030 in. in diameter. Molybdenum disulfide was used as the die lubricant. The extrusion was done in a vacuum of about 10-4 torr to reduce reaction of the neptunium with atmospheric gases. British workers3 at Harwell have extruded neptunium under similar conditions. The force required to extrude 0.010-in.-diameter wire at the rate of 4 in. per min was 6000 lb, as measured with an electrical load cell. Wire 0.020 in. in diameter was extruded with a force of 4700 lb at a rate of 2 in. per min, and wire 0.030 in. in diameter was extruded with a force of 4000 lb at a rate of 1.3 in. per min. An extrusion constant, c, can be computed from the measured forces, P, for the equation4 P = c log-A/a where A/a is the extrusion ratio or the ratio of the cross-sectional areas of the container and the

Jan 1, 1965

By C. O. Hawk

A PART of the Bureau of Mines effort to improve the conversion of coal to liquid fuels, batch autoclave tests were made on the hydrogenation of bituminous coal by a dry method, which featured charging the autoclave with dry ingredients only-coal, catalyst, and hydrogen. This innovation, which omitted the liquid vehicle used in earlier work, limited the products to those made from the coal charged. The effects of the common process variables (catalyst, hydrogen pressure, temperature, and residence time) were studied. Tin catalysts showed the highest activity in the widest variety of forms and were the easiest to disperse; dry mixing in the autoclave during the heating-up period usually sufficed. Ammonium molybdate, on the other hand, was inactive when dry mixed, but it compared favorably with the best catalysts known when applied by impregnating the coal with a solution of a molybdenum compound. As a group, metal naphthenates were the most effective; in fact, molybdenum naphthenate was the most active catalyst the Bureau tests disclosed. One-hundredth of a percent of molybdenum in this form (calculated as the metal in weight-percent of maf coal) induced 90-percent conversion of coal. However, because of their high cost, naphthenates have as yet only technical significance in coal hydrogenation. Long residence time and high reaction temperatures tend to increase the amount of thermal decomposition products formed (light hydrocarbon gases and/or char). High hydrogen pressure favors the production of liquids.

Jan 1, 1965

By K. C. Dean

This report is the first of a series concerned with processes for producing magnesium. These reports will evaluate metallothermic, carbothermic , and electrolytic production methods, and will furnish a cost basis for comparing the processes. Areas deemed most promising for future research will be delineated for each procedure. This report presents briefly the history of the metallothermic process, and describes the operations of the Defense Plant Corp. (DPC) plants that employed the process. A hypothetical plant designed to produce 12,000 tons of magnesium per year, using ferrosilicon as a reductant, is described, and raw materials, energy, and major equipment requirements are estimated. Several process modifications are suggested for future research.

Jan 1, 1965

By R. W. Hertzberg, F. D. Lemkey, J. A. Ford

The technique of unidirectional solidification has been applied to the A1-AI3Ni and A1-CuAl2 ezltectic alloy systems; the controlled microstructure of A1-A3Ni consists of parallel A13Ni whiskers emhedded in an aluminum matrix while the Al-CuAl2, system solidifies as parallel alternate lamellae of aluminm and CuAl2. Mechanical tests (tension and flexure) have shown that the particle-matrix interface bond formed during unidirectional solidification allowes for efficient load transfer from the matrix to the reinforcing phase. Strength and fracture characterstics of the alloys were studied as a function of phase orientation; the tensile strength of controlled Al-Al3Ni samples was 43,000 psi (three times greater than that of as-cast specime~s). The strength of the Al-CIA2, cutectic was studied as a function of lamellae-flexure stress-axis orientation using a microbend apparatus. A twofold increase in outer fiber stress was observed as the lamellae were rotated from a position of no reinforcing (perpendicular to the stress axis) to one of maximum reinforcing (parallel to the stress axis), The brittle reinforcing constituent in each alloy (A13Ni and CuAl2) was observed to he the nucleating phase for fracture. It is to be concluded from this investigation that unidirectionally solidified eutectic alloys have a potential use as reinforcing coniposite) materials. In a recent review article, Chadwick1 has described the work of many investigators in the area of controlled solidification of binary eutectic alloys. Thus far, more than twenty eutectic alloys have been unidirectionally solidified to produce structures consisting of two phases in the form of alternating lamellae or as whiskers embedded within a continuous matrix; in either case, the phases are aligned parallel to the growth direction. In particular, Kraft and Albright2 have shown that the Al-CuA1, eutectic alloy exhibits a lamellar microstruc- ture as a result of unidirectional solidification while Lemkey, Hertzberg, and Ford3 have studied the A13Ni whisker-aluminum matrix morphology in the A1-A13Ni system. Whether these alloys could exhibit reinforcing behavior would have to depend upon the strength and volume fraction of the reinforcing phase (AI3Ni and CuA12) and the nature of the bond between the reinforcing phase and the matrix. Hertzberg and Kraft4 have shown that the interface bond between chromium whiskers and a copper matrix in unidirectionally solidified Cu-Cr is particularly good while Lemkey and Kraft5 have reported chromium-whisker tensile strengths in excess of 1,000,000 psi. However, with the chromium volume fraction being less than 2 pct, no reinforcing behavior was displayed by the Cu-Cr alloy.6 In view of the encouraging results concerning the good interfacial bond and high strength of the reinforcing phase in the Cu-Cr system and preliminary mechanical test data reported by Lemkey et al.3 for the A1-A13Ni system, the A1-CuA1, and A1-A13Ni eutectic alloys containing 50 and 10 vol pct, respectively, of the reinforcing phase give promise of possessing mechanical reinforcing behavior. Based on this premise, the objective of the investigation was to study the strength and fracture behavior exhibited by these anisotropic microstructures. EXPERIMENTAL PROCEDURE Controlled Solidification Procedure. An extensive description of the technique of unidirectional solidification has been presented elsewhere.' However, the pertinent details for each eutectic system studied are discussed below. Al-A13Ni System. Several master heats of this alloy were prepared by vacuum-induction melting in an A12O3crucible and casting in SiO2 mold or by induction melting in alumina crucibles under argon. The initial heats were prepared from 99.99 pct A1 and 99.99+ pct Ni, while later heats used 99.999+ pct A1 and 99.99+ pct Ni. Specimens of these master heats were unidirectionally solidified using induction and resistance heating sources and argon atmospheres at growth rates from 1.1 to 28.7 cm per hr. The thermal gradients in the liquid were controlled in the range of 26" to 36°C per cm for these runs. Al-CuA12 System. The master heat and controlled

Jan 1, 1965

By D. S. Tomalin, D. F. Stein

The effect of reducing oxygen to low concentrations on the fracture of high-purity iron single crystals has been examined at 78° and 20°K. It is found that iron single crystals grown by the strain-anneal method usually contain a few occluded grain boundaries which may become embittled in the presence of oxygen, thereby nucleating cleavage fractures. High purity with respect to interstitial elements was found to inhibit twinning and evidence is presented for an orientation dependence of the resolved yield stress. Deformation occurred by slip rather than twinning at both temperatures of testing with elongations of as much as 9 pct at 20°K. THE fracture properties of iron single crystals have been observedl-3 to be a function of temperature, orientation, and purity. Allen, Hopkins, and McLennan1 demonstrated that at 78°K iron single crystals became increasingly brittle as the tensile axis approached the (001) pole of the stereographic unit triangle. Iron crystals with the tension axis near a (001) pole were completely brittle and orientations near the (011)-(111) boundary were very ductile, achieving a 100 pct reduction in area prior to fracture. Later work of Biggs and pratt2 and of Edmondson3 demonstrated that by reducing the carbon content of the single crystals the transition between brittle and ductile failure at 78°K could be shifted to orientations nearer the (001) pole. Ed-mondson went further and pointed out that any mechanism which tended to increase the yield strength of the iron (i.e., carbon addition, pre-strain) also increased the tendency for brittle behavior at 78°K. Thus by a reduction of carbon content Biggs and Pratt were able to obtain ductile behavior to within 20 deg of the (001) pole, and Ed-mondson was able to obtain ductile behavior to within 26 deg of the (001) pole. Edmondson's material had a total interstitial content (carbon, oxygen, and nitrogen) of approximately 60 ppm and, although Biggs and Pratt reported no analysis, indications were that their iron contained comparable impurities. Stein, Low, and seybolt4 purified iron single crystals to a total carbon, oxygen, and nitrogen content of approximately 20 ppm. They observed a lowering of the yield stress with this increased purity, and thus one might have expected an observation of increased ductility. Although they tested specimens of orientations which the previous workers had indicated should be ductile, the crystals failed at a 78°K in a brittle manner with little elongation. Stein noted,' however, that about 90 pet of the failures could be traced in origin to occluded grains. Allen et al.1 and Edmondson3 do not report examination of their cleavage surfaces, but Biggs and pratt2 reported that microscopic examination of the cleavage surfaces of many of their specimens revealed the presence of small occluded grains. Honda and cohen6 and Keh7 have also observed the initiation of fracture at occluded grains in iron single crystals. Therefore, the additional complication of occluded grains must be considered in studying the properties of iron single crystals and the origin of fractures determined if the ductility exhibited by the crystals is to be considered meaningful. Various investigators8-12 have studied the effects of impurities on grain boundaries in high-purity polycrystalline iron. Rees and Hopkins10 showed that the addition of oxygen to low-carbon (0.002 pet) iron weakened the grain boundaries, causing a shift from transcrystalline to intercrystalline fracture and a progressive decrease on the brittle-fracture stress with increasing oxygen content. In addition, it has been shown by Low and Feustel11 that the addition of carbon to polycrystalline iron containing oxygen eliminated grain boundary brittleness. Thus, oxygen can embrittle grain boundaries in high-purity polycrystalline iron, but the addition of an appropriate amount of carbon can eliminate the oxygen-induced brittleness. The oxygen content (19 ppm) of the iron "single crystals" employed by Stein el al. was large enough to suspect impurity effects at the occluded grain boundaries. Allen et al.1 Biggs and pratt,2 and Edmondson3 may have masked any occluded grain problem in their specimens considering the relatively high carbon levels they employed. stein13 demonstrated that the addition of as little as 0.9 ppm C to previously purified (less than 5 x 10-3 ppm C) "single crystals" would increase the elongation from a few percent to more than 20 pet at 78°K and the fracture was not associated with grade boundary initiation.

Jan 1, 1965

By A. T. Harris

Ground quartzite, known in the industry as amorphous silica, is produced from a quartzite deposit near Honey Brook, Pa., by George F. Pettinos, Inc., of Bala-Cynwyd, Pa. The quartzite is mined by the open pit method and processed in a mill at the mine. The operation regularly produces five standard grades of sand and one grade of crushed stone; however, the company accepts special orders and will produce material to meet the customer's specifications. Beneficiation (chiefly crushing and screening) is controlled by laboratory screen tests on samples taken during preparation of the sand. The chief uses of the sand are for foundry operations, furnace lining, concrete aggregate, and Other specialized uses. The quartzite in this deposit is of uniform composition and does not require control by chemical analysis. However, for special purposes, analysis will be furnished.

Jan 1, 1965

By Tilman M. M.

The effects of substituting cobalt for nickel on the acid corrosion resistance of two types of austenitic stainless steel were determined. Cobalt substitutions to a maximum 2.2 weight-percent were made in types 302 and 309 stainless steels. Total immersion corrosion tests were made in 10 volume-percent hydrochloric acid, and boiling-acid tests were conducted in 65 weight-percent nitric acid and in undiluted glacial acetic acid. For modified type 309 in acetic acid, corrosion rates decreased for additions greater than 0.57 weight-percent cobalt. Corrosion rates increased as cobalt was increased up to about 1 weight percent for modified type 302 in nitric and hydrochloric acids and for modified type 309 in nitric acid, but these rates decreased with a further increase in cobalt content. A gradual increase in corrosion rates with increasing cobalt content was shown for type 302 in acetic acid and for type 309 in hydrochloric acid. Cobalt substitutions in larger amounts (above a ratio of 8 Ni to 1 Co) may increase the corrosion resistance of the austenitic stainless steels.

Jan 1, 1965

By J. L. Lytton

The flow-stress recovery of high-purity aluminurn following a 10 pct tensile prestrain was studied in terms of a fractional flow-stress recovery parameter fr. The flow-stress recovery behavior was related to the dislocation arrangements using transmissiort electron rnicvoscopy. During recovery at 120° and 160°C, nearly stable strength levels were attained, the strength level for 120°C recovery being greater than that for 160°C. This stabilization of flow stress was related to the formation of meta-stable dislocation networks bounding nearly perfect cells. Both network formation and the annealing of dislocation loops were found to be recovery mechanisms, and the stronger metastable strength level joy 120°C recovery was related to a smaller average cell size. Analysis of the networks was consistent with the reaction of sets of dislocations with a/2 (110) Burgers vector to give product Burgers DURING isothermal annealing of cold-worked metals, a degree of softening occurs without re-crystallization, and the processes responsible for this change are termed recovery processes. During recovery annealing, the dislocations generated during cold work become rearranged into low-energy configurations, and as much as 50 pct of the stored energy is released."' The relationship between this rearrangement of dislocations and mechanical behavior is of considerable importance, since the dislocation substructures formed during recovery provide a significant degree of low-temperature strength3j4 and can favorably alter the course of primary creep at high temperatures.4 The purpose of the present study was to relate the flow-stress recovery behavior of high-purity aluminum to the substructural modifications that occur. Electron transmission microscopy was therefore employed for direct observation of dislocation substructures at various stages of recovery following 10 pct prestrain. Several investigators5-' have proposed that dislocations can become rearranged or lost during the preparation of thin foils. It was found early in the present study that the dislocation structures in the thicker regions of the foils changed in a systematic way during the course of recovery. Therefore, it is unlikely that substantial losses or rearrangements occurred during thinning. This point will be discussed in more detail later. The results of various investigators indicate that recovery processes in fcc metals can result in release of 50 pct or more of the total energy stored in the as-prestrained metal, this percentage decreasing with increasing prestrain.' Alloying elements or impurities tend to increase this percentage. The release of stored energy of fcc metals during recovery appears to occur by 1) annealing of point defects if the deformation occurred at sufficiently low temperaturesg and 2) rearrangement of dislocations into low-energy Configurations.1,2In bcc metals, the annealing of dislocation loops has also been observed during recovery after prestrain,10-12 and it has been proposed that this is a recovery mechanism for unidirectionally strained fcc metals.' The density of dislocations in bcc metals has not been observed to decrease appreciably during recovery,10 although the formation of regular dislocation networks has been observed. has shown that the formation of such networks can result in elimination of long-range stresses and can lead to significant release of stored energy without dislocation annihilation. It might thus be expected that network formation is a significant recovery mechanism in fcc metals, although extensive network formation has apparently not been reported in controlled recovery experiments. The formation of sub-boundaries in aluminum has been observed by various investigators13'17 during recovery studies of aluminum, but the structure of these boundaries was not resolved. In this regard, it is significant to note that Bailey and Hirsch,' using transmission electron microscopy, detected no network or sub-boundary formation during recovery of 99.99 pct Ag. Furthermore, Clarebrough et al.2 found no such rearrangements during recovery of copper. EXPERIMENTAL PROCEDURE The high-purity aluminum used in this investigation was obtained in the form of 0.125-in.-thick sheet. Spectrographic analysis revealed that the sheet was 99.995 pct A1 with the following weight-percent impurities: 0.001 Cu, 0.002 Fe, 0.001 Si, and 0.0004 Mg. The as-received sheet was in the heavily cold-rolled condition. The as-received sheet was cold-rolled at room temperature to 0.040-in.-thick sheet in the longitudinal direction, which was the original rolling

Jan 1, 1965

By Nicholas J. Grant, Yoichi Ishida, Arthur W. Mullendore

An inert particle -marker technique was developed to provide a direct measurement of grain boundary sliding during creep in tile interior of aluminum specimens. Groin boundary sliding in the interior as measured by this technique was found to be nearly the same or slightly lower than that measured on the surface. These data disagree with those obtained by the grain-counting technique developed by W. A. Rachinger. In tests where both techniques were used, the grain-counting technique gave large and variable values of grain boundary sliding. It is shown that the grain-counting technique gines erroneozcs results because of a preferred direction of grain growth during creep. A question which has long plagued those who study grain boundary creep is whether or not surface measurements yield a true representation of the deformation in the interior of a specimen. The first attempt to measure grain boundary sliding in the interior of a creep specimen was made by Rachinger.1 His technique is based on the measurement of average grain diameters, both parallel and perpendicular to the tension axis, followed by a calculation of the grain elongation from these measurements. The difference between total elongation, Et, and the calculated grain elongation, Eg, is considered to be the result of grain boundary sliding, Egb. Surprisingly large values of Egb/ Et (90 pct) came out of creep tests of pure aluminum at temperatures above 250°C (480°F), utilizing the Rachinger technique. This value is very much larger than the values of 8 to 15 pct measured by numerous investigators on the surface of a specimen. Values obtained on the surface by Rachinger, however, were consistent with those measured by the displacement of reference scratches. Chaudhuri and Grant2 repeated the Rachinger method for A1-10 pct Zn, and found the same large values of Egb/Et inside the specimen. However, from purely geometrical considerations, grain boundaries cannot slide without grain deformation; therefore, they questioned the validity of Rachinger's grain-counting method. Several authors2,3 have suggested that grain boundary migration during high-temperature deforma- tion may tend to restore the equiaxed grain shape in order to minimize interfacial energy. Rachinger4 tested this hypothesis and found that it did not hold. Grains elongated by rapid extension retained their elongated shape during a subsequent slow creep test. It appears that some other factor was responsible for the abnormally high values of .Egb/El. McLean and Gifkins5 made a survey of the effect of grain size on the ratio Egb/ Et, and proposed that the high values were the consequence of a small grain size. They failed to explain the low value of Egb/Et which Rachinger observed on the surface of the small grain size specimens, and suggested that the surface effect on the value of Egb/Et does not always occur. Many of the disagreements arising from Rachinger' s work stem from the fact that there was only one method of estimating grain boundary sliding in the interior of a specimen, and that method was of an indirect nature. If a marker line of some sort could be introduced inside of the specimen, one could make measurements just as clearly as on the surface. In the present investigation, the technique utilizes a layer of finely dispersed oxide particles inside the specimen introduced by hot press-bonding of two pieces of aluminum. Rachinger attempted a similar technique but with the oxide distribution he obtained there was so much interference with grain boundary motion that quantitative measurements were not attempted. MATERIALS AND EXPERIMENTAL PROCEDURE A) Materials Preparation. Two pure aluminum rods (impurity content in percent: Si, 0.002; Cu, 0.004; Fe, 0.002; Mg, 0.000: Zn, 0.000; V. 0.001) 1 in. diameter by 2 in. high were jacketed end to end in a 4-in.-diam cylinder of commercial-purity aluminum, 4 in, high, which had a l-in.-diam hole. The l-in.-diam mating surfaces of the two pure aluminum rods had been electropolished initially. This interface provided the oxide-film internal -marker plane after the hot press-bonding process, see Fig. 2. The composite was annealed for 1 hr at 900 F and hot upset more than 50 pct reduction in height in one step. The resulting slab was then rolled to 1/2 in. thickness; the pure aluminum test material was cut out and annealed at 900°F for 1 hr and cold cross-rolled to 1/8 in. thickness. The sheet was machined into specimens with a 1/8-in.-square cross section and a 1/2-in. gage length. The following heat treatment was given the specimens: Specimen 5A series: annealed at 1000°F for 5 min for grain-size control and then cooled to 700°F and held for 15 hr for stabilization.

Jan 1, 1965

By H. A. Domian, H. Biloni, G. F. Bolling

Jan 1, 1965

By L. B. Pankratz

Heat contents, measured above 298.15° K, and derived entropy increments are presented in tabular and equation form for the two crystalline forms of zinc sulfide (sphalerite and wurtzite) and for four solid solutions of iron and zinc sulfides having the compositions Zno.,,6Fe0.302S, Zno.750Fe0.250S, Zno.650Fe0.3505, and Zno.498Feo.502S.

Jan 1, 1965

By James D. Brown

The Bureau of Mines has written a computer program in FORTRAN to facilitate the calculation of concentrations from X-ray intensities in electron probe microanalysis. Philibert's absorption and Castaing's secondary fluorescence corrections are used; no atomic number correction is included. Background and dead time corrections are applied to the data before calculating the relative intensities. Data from any type of electron probe microanalyzer can be used with the program.

Jan 1, 1965

By J. B. Gayle

The Bureau of Mines studied the effects of air oxidation on the recovery of float coal. Both batch-and continuous-type tests were made on six bituminous coals, representing the range in rank of coals now commercially used for carbonization, and on one anthracite coal. The effects on flotation recovery of oxidation at 1000 C for periods up to 50 days were investigated using an alcohol-type frother and a kerosine-pine oil reagent. Two series of release analysis tests were made, using one medium-volatile bituminous coal. Float coal recovery was adversely affected by oxidation in all tests where the alcohol-type frother was used. Conversely, a small degree of oxidation improved recovery with kerosine-pine oil frother for some of the coals in continuous tests. Prolonged oxidation (beyond about 14 days) adversely affected float coal recovery for all coals, the effect being more pronounced for batch-type tests and for tests using alcohol-type frother. Reagent selectivity for the rejection of both ash forming and sulfur bearing minerals was reduced by oxidation. Severe reduction of reagent selectivity required only about 3 days' oxidation for alcohol-type frother but more than 10 days' oxidation when the kerosene-pine oil reagent was used.

Jan 1, 1965

By B. W. Howlett, M. B. Bever, Somnath Misra

The heats oj- formation at 0°C of the compounds AuSn,, AuSn2, AuSn, and the £ phase were measured in a metal -solution calorimeter with liquid tin or a liquid Sn-Bi alloy as solvent. The melting point, heat of fusion, and heat capacities near the melting point of- the compound AuSn in the solid and liquid state were measured in a constant temperature gradient calorimeter. The free energy and entropy of formation of the compound AuSn at its melting point and at 298 °K were calculated from the experimental results and published data. The heats of formation are discussed in relation to the nature of the compounds. The heat capacity below the melting point, heat of fusion, and entropy of fusion of AuSn are interpreted in terms of processes oc-curring before melting. The atomic arrangement in liquid Au-Sn alloys and the bonding in the intermediate phases of. the Au-Sn system are discussed in the light of the measured thermodynamic properties. THE available thermodynamic information on the intermediate phases in the Au-Sn system consists of the heats of formation of the compounds AuSn4, AuSn2, and AuSnly2 and of one composition of the < phase2 besides values of the heat content of the compound AuSn from 0" to 635".&apos; However, the heats of formation refer to different temperatures ringing from 90" to 450°C. Also, the reported error limits of some of the values are large and several inconsistencies are apparent. In the investigation reported here the heats of formation of the compounds AuS-, AuSnz, and AuSn and of three compositions of the < phase were determined for a single reference temperature of 0°C by liquid metal-solution calorimetry. The compound AuSn, which is the only congruently melting intermediate phase in this system, was further investigated in a constant temperature gradient calorimeter by measuring its heat of fusion, melting point, and heat capacity in the solid and liquid states near the melting point. From these data and published free energies of the liquid of composition Au~n,&apos; the free energies of formation of the compound AuSn at the melting point and at 298°K were calculated. The results shed light on the solid-liquid transition of AuSn and on the atomic bonding and state of association of gold and tin in the solid and liquid phases. 1) EXPERIMENTAL PROCEDURES 1.1) Preparation of Samples. Stoichiometric amounts of gold and tin, each 99.99+ pct pure, were melted in evacuated Vycor capsules (12 mm ID). The melts were maintained approximately 150°C above the liquidus for about 12 hr and shaken repeatedly. Samples of the compound AuSn were cooled slowly to room temperature. Melts of the other phases, all of which solidify by peritectic reactions, were transferred to the narrow end (5 mm ID) of the capsule, which was then quenched into iced brine. The solidified samples were annealed in the unopened capsules for 10 days at 30" to 50° C below the respective solidus temperatures. The absence of microsegregation and second phases was confirmed by metallographic examination. At least two batches of each composition were prepared. 1.2) Solution Calorimetry. The heats of formation were determined by liquid metal-solution calorimetry. In this technique, the difference between the heat effects on dissolution in a liquid metal, or alloy bath, of the compound and a mechanical mixture of its annealed components, adjusted for changes in composition of the bath, is the heat of formation of the compound at the temperature from which the samples are added. Details of the equipment and technique have been described."&apos; A tin bath at 300" or 350°C was used with the compounds AuSn,, AuSnz, and AuSn. The high gold content of the £ phase would have caused it to dissolve with an appreciable exothermic heat effect. In order to achieve thermal compensation, the samples were added from 0°C to a bath at 350°C consisting of 66.2 wt pct Bi (99.999+ pct pure), balance Sn (99.99+ pct pure). This solvent gives thermal compensation because gold dissolves exothermically in tin and endothermically in bismuth. The calorimeter was calibrated by adding from 0°C approximately 0.015 g-atom of the solvent.

Jan 1, 1965

By S. J. Gasior

A method for destroying the caking properties of bituminous coal was developed by the Bureau of Mines. Coal is treated in a fixed bed by heating through its plastic range under controlled temperatures in mildly oxidative atmospheres composed of inert gas and/or steam containing about 1 volume-percent oxygen. High-volatile A (hvab) and high-volatile B (hvbb) and low-volatile bituminous (lvb) coals in the size range 1/8 to 1-1/2 inches were successfully treated at 0 (atmospheric pressure) to 300 psig in static beds 6 to 18 inches deep. Conditions of treatment depended on the coal and ranged from 80 to 200 minutes at 350° to 510° C. Char produced in this manner from hvab coal was gasified with steam at 800° C and 100 psig in a fixed bed in one series of tests and in other tests was exposed to hydrogen in a dilute co current free-falling-bed system at 750° C and 3,000 psig without agglomerating.

Jan 1, 1965

By George R. Schottler

The objective of this research is to find the extent of the range of applicability of previously developed statistical methods for determining grade and tonnage of ore to bedded uranium deposits. Uranium assays obtained from gamma-ray logs of exploratory drill holes are used to compute grade and tonnage of ore in the deposit by a standard polygonal method and by statistical analysis. The results obtained by the two methods are compared. The uranium-assay frequency distributions are shown to be lognormal and a simple transformation permits the use of standard normal curve statistics. The effects on the assay frequency distributions of stratified sampling, a required minimum mining thickness, and increased assay-interval length are investigated. The addition of low-grade mineralization to make up the required minimum mining thickness results in a distinct change in the skewness of the assay frequency distribution. Any statistical inference regarding grade-tonnage relationships that will be produced, using the minimum mining thickness, should be made on the basis of this "revised" assay frequency distribution.

Jan 1, 1965

By Malcolm T. Hepworth

RECENT interest in thermoelectric devices has been directed toward studies of the properties of thermoelectric materials of semiconducting solid compounds with little attention given to ionic and semiconducting liquids such as aqueous solutions, fused salts, and mattes. One type of thermoelectric system is the thermocell: a nonisothermal galvanic cell with two identical electrodes at different temperatures connected by an electrolyte bridge. An electromotive force, v, is generated which is a function of the electrode reactions and the properties of the electrolyte according to the Eastman&apos; equation: where S* is the entropy change of the system arising from the electrode reactions and by heat transferred by ion migration and by thermal conduction. The quantity nF is the product of equivalents passed and Faraday&apos;s constant. A value of S* of 23.06 cal per "C is equivalent to 1 mv-Faraday per "C. The symbol, a, is used for dV/dT in analog to the See-beck coefficient of solid-state thermoelements. de Bethune2 has calculated the temperature coefficients of the electromotive force of a large number of nonisothermal aqueous cells from measurements on the nonisothermal temperature coefficients of the standard hydrogen electrode, combined with data on the isothermal temperature coefficients of half-cells tabulated in the literature. Values of these coefficients (a) in de Bethune&apos;s compilation ranged up to 3 mv per C. In particular he reported a value of +2.059 mv per "C at 25&apos;C for the cell: Fe (aqueous, unit activity) (aqueous, unit activity) written for the hot-electrode reaction. The positive sign indicates that the hot electrode is positive (an "n-type thermocell"). In analog to a solid-state p-n system, it would be possible to couple two thermocells together to form a system in which the figure of merit could be calculated by adding the temperature coefficients according to the relationship described by offee:&apos; where a is the Seebeck coefficient in volts per "C, p is the specific resistivity in ohm-cm, and K is the thermal conductivity in watts per cm "C. Even though ionic systems have rather high electrical resistivities compared with semiconducting and metallic systems, it was felt that a preliminary study of one ionic system should be made to establish some basis for evaluating the possibility of a p-n thermocell for energy conversion. Accordingly the Fe", Fe"&apos; system was studied as a possible component for a p-n system. A glass system was constructed consisting of two vertical water-jacketed tubes connected by a horizontal tube, Fig. 1. Platinum-black electrodes 1 cm by 1 cm in dimension were inserted in each vertical tube with thermometers to register the electrode-compartment temperatures. The temperature of the electrode compartments was controlled by circulating water from thermostatted baths around the electrode compartments. The electromotive force of the cell was then read by a potentiometer for zero current as a function of the temperature of the hotter electrode. Current output of the cell for varying external loads was also measured. The cell resistance was measured by means of a bridge circuit with 10,000 cps signal and oscilloscope. Resistance measurements were converted to specific resistivity by calibrating the cell with a solution of known conductivity.

Jan 1, 1965

By J M. Gibbs

Craigmont Mines Limited mine 50,000 tons of ore and waste per day from the open pit at Merritt, British Columbia. An electric-powered "down-the-hole" drill, a diesel-powered rotary drill and two electric-powered rotary drills have been used. All primary drilling, as a result of cost and operating experience, is now performed with two electric-powered rotary drills. Trials with various loading techniques have increased the amount of AN-FO and decreased the amount of commercially prepared slurries used for primary blasting. Approximately 95 per cent of the primary blasting is accomplished with AN -FO, mixed at the hole. Introduction THE Craigmont mine is located near the village of Merritt, B.C., 240 miles northeast of Vancouver. The concentrator has been in production since September of 1961. Craigmont is a combined open-pit and underground operation. To date, slightly more than 95 per cent of the mill feed has been mined from the open pit. As underground development proceeds, the ore requirements from the open pit will decrease. The average milling rate from September, 1961, to April, 1964, was approximately 4,900 tons per day.

Jan 1, 1965